Method for preparing base glass by vacuum melting-atomized water quenching of high-calcium low-iron AOD stainless steel slag
The method of preparing basic glass through vacuum melting and atomization water quenching of high-calcium, low-iron AOD stainless steel slag solves the problem of insufficient harmless treatment and resource utilization of AOD stainless steel slag, achieves efficient harmless treatment and resource utilization, and improves the performance and application range of glass.
Patent Information
- Application Number
- CN202510910055.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-02
- Publication Date
- 2025-09-16
AI Technical Summary
The existing harmless treatment and resource utilization of AOD stainless steel slag are insufficient, especially the efficient removal of toxic substances hexavalent chromium (Cr6+) and divalent nickel (Ni2+), and the comprehensive resource utilization rate is low.
The method of preparing basic glass by vacuum melting and atomizing water quenching of high-calcium and low-iron AOD stainless steel slag is adopted. By adding dopants such as SiO2, MgO, ZrO2 and nano-Al2O3, gradient heating and melting modification is carried out in a vacuum environment, and rapid cooling is carried out by atomizing water quenching to prepare high-performance basic glass.
It achieves efficient and harmless treatment of AOD stainless steel slag, improves resource utilization, reduces energy consumption, enhances the compressive strength, surface hardness and thermal stability of glass, and broadens the scope of industrial application.
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Abstract
Description
Technical Field
[0001] The invention relates to a method for preparing basic glass by vacuum melting-atomizing and water quenching of high-calcium and low-iron AOD stainless steel slag, and belongs to the technical field of basic glass. Background Art
[0002] As the main by-product of stainless steel production, AOD stainless steel slag contains not only conventional elements such as iron (Fe), silicon (Si), magnesium (Mg), and calcium (Ca), but also valuable metal elements such as nickel (Ni), chromium (Cr), and molybdenum (Mo). However, some metal elements in stainless steel slag are environmentally unstable, especially under open-air storage or landfill disposal conditions, and the toxic substance hexavalent chromium (Cr 6+ ) and divalent nickel (Ni 2+ ) is prone to dissolution, posing a potential threat to the ecological environment and human health. Therefore, stainless steel slag possesses both secondary resource value and environmental pollution risks. Currently, research on the harmless treatment and resource utilization of AOD stainless steel slag is still in its early stages, with related research results largely limited to laboratory-scale studies, and the comprehensive resource utilization rate remains at only approximately 20%. Given this situation, developing technologies for the harmless treatment and resource utilization of AOD stainless steel slag has important practical significance and application value. Summary of the Invention
[0003] In response to the problems of harmless treatment and insufficient resource utilization of existing AOD stainless steel slag, the present invention proposes a method for preparing basic glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag. Vacuum melting is used to reduce energy consumption and solidify Cr, and the basic properties of the basic glass are improved by adding a doping modifier, thereby achieving efficient harmless treatment of AOD stainless steel slag and large-scale production of basic glass.
[0004] A method for preparing basic glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag, comprising the following specific steps: (1) Grinding and sieving high calcium and low iron AOD stainless steel slag to obtain stainless steel slag powder; (2) Measure the chemical state and content of metal elements Cr, Ni, Fe, Mn, Ca, and Mg in stainless steel slag powder; (3) According to the chemical state and content of the metal elements Cr, Ni, Fe, Mn, Ca, and Mg, additives SiO2, MgO, and borax are added to the stainless steel slag powder to obtain mixed material A, and then ZrO2 and nano-Al2O3 are added to obtain mixed material B; (4) Under vacuum conditions, the mixed material B is subjected to gradient temperature increase and melting modification to obtain high-temperature modified slag; (5) Atomized micron-sized water droplets are sprayed onto the melt in a direction to perform atomized water quenching, so that the high-temperature modified slag is rapidly cooled to a temperature below 800°C within 1 to 10 seconds to obtain basic glass particles.
[0005] Preferably, the particle size of the stainless steel slag powder in step (1) is less than 20 mesh.
[0006] In terms of mass percentage, the high-calcium, low-iron AOD stainless steel slag in step (1) contains 40-60% CaO, 10-35% SiO2, 1-5% Al2O3, 2-15% MgO, and 0.1-2% Fe.
[0007] Calculated by mass fraction of stainless steel slag powder, step (3) SiO2 10-80%, MgO 20-80%, borax 1-5%.
[0008] Preferably, the theoretical amount of borax added in step (3) is 20%±0.5% of the total mass of the metal elements Cr, Ni, Fe, and Mn, and the amount of Cr in the chemical state of Cr is determined. 6+ When it accounts for more than 5% of the total Cr, the amount of borax added is increased by 20%; according to the content of metal elements Ca and Mg, the amount of SiO2 and MgO added is adjusted so that the molar ratio of CaO, MgO, and SiO2 is (0.8~1.2):1:(1.5~2.5), the amount of ZrO2 added is 1~5% of the total mass of the mixture A, and the amount of nano-Al2O3 added is 2~8% of the total mass of the mixture A so that the mixture meets the composition range of diopside CaMgSi2O6.
[0009] Preferably, the step (4) comprises the following steps: uniformly heating the temperature to 1000-1200°C at a heating rate of 10-15°C / min and keeping the temperature for 30-150 min; then uniformly heating the temperature to 1250-1500°C at a heating rate of 6-8°C / min and keeping the temperature for 30-120 min.
[0010] Preferably, the particle size of the basic glass particles in step (5) is 1-5 mm.
[0011] The beneficial effects of the present invention are: (1) The present invention uses high-calcium, low-iron AOD stainless steel slag as the raw material for preparing glass, breaking through the traditional process's limitation on the iron content of the raw material, broadening the range of steel slag that can be used in production, and improving resource utilization; (2) The amount of additives such as silicon dioxide (SiO2) and magnesium oxide (MgO) added in the present invention is relatively small, and the melting temperature of the vacuum furnace is reduced by 10%-15% compared with the traditional electric furnace. The oxidation of trivalent chromium is suppressed in the vacuum environment, and the solidification of Cr is effectively achieved; (3) The present invention greatly improves the compressive strength, surface hardness and thermal stability of glass by adding dopants such as zirconium oxide, borax and nano-alumina particles, making it have a wider range of industrial applications; (4) The present invention uses atomized water quenching to rapidly cool the glass, thereby preventing the formation of a crystal structure and enhancing the activity of the slag. The addition of doping groups greatly improves the basic properties of the glass. The prepared diopside-type basic glass has been greatly improved in terms of hardness, density, high temperature resistance, thermal stability, mechanical strength and chemical stability, and can meet the requirements of more demanding industrial application environments. BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Figure 1 is the XRD pattern of the base glass of Example 1; Figure 2 The SEM-EDS image and physical image of the base glass of Example 1 Figure 3 The adsorption curve and pore size distribution of the base glass of Example 1 are shown in FIG. Figure 4 is the XRD pattern of the base glass of Example 2; Figure 5 The physical image and SEM-EDS image of the base glass of Example 2; Figure 6 is the XRD pattern of the base glass of Example 3; Figure 7 This is the XRD pattern of the base glass of Example 4. DETAILED DESCRIPTION
[0013] The present invention will be further described in detail below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the contents described above.
[0014] Example 1: A method for preparing basic glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag, the specific steps are as follows: (1) Grind and sieve the high calcium and low iron AOD stainless steel slag to obtain stainless steel slag powder with a particle size of less than 15 mesh; (2) Measure the chemical state and content of metal elements Cr, Ni, Fe, Mn, Ca, and Mg in stainless steel slag powder, as shown in Table 1; Table 1 Chemical states and contents of metal elements Cr, Ni, Fe, Mn, Ca and Mg in stainless steel slag powder ; Determination of Cr in the chemical state by XPS 6+ 4% of total Cr; (3) According to the chemical state and content of the metal elements Cr, Ni, Fe, Mn, Ca, and Mg, the additives SiO2, MgO, and borax are added to the stainless steel slag powder to obtain a mixture A, and then ZrO2 and nano-Al2O3 are added to obtain a mixture B; specifically, the theoretical addition amount of borax is 20%±0.5% of the total mass of the metal elements Cr, Ni, Fe, and Mn; the addition amounts of SiO2 and MgO are adjusted according to the content of the metal elements Ca and Mg so that the molar ratio of CaO, MgO, and SiO2 is 1.06:1:2.20, the addition amount of ZrO2 is 3% of the total mass of the mixture A, and the addition amount of nano-Al2O3 is 5% of the total mass of the mixture A so that the mixture meets the composition range of diopside CaMgSi2O6; Calculated by mass fraction of stainless steel slag powder, the additive amounts of this embodiment are: SiO2 45%, MgO 25%, and borax 2.5%; (4) Under a vacuum environment (5 Pa), the mixed material B is subjected to gradient temperature increase melting modification to obtain a high-temperature modified slag; the gradient temperature increase melting modification method is as follows: uniformly heating the material to 1000°C at a heating rate of 10°C / min and keeping the temperature for 30 minutes, then uniformly heating the material to 1350°C at a heating rate of 8°C / min and keeping the temperature for 120 minutes; (5) Directly spraying atomized micron-sized water droplets onto the melt for atomized water quenching, so that the high-temperature modified slag is rapidly cooled to a temperature below 800°C within 1 to 10 seconds to obtain basic glass particles; The XRD pattern of the basic glass particles in this embodiment is shown in Figure 1 ,from Figure 1 It can be seen that the XRD pattern does not show any sharp diffraction peaks (especially in the high-angle region of 10-90°), indicating that the sample has not undergone obvious crystallization and is in an ideal basic glass state; Figure 2 The SEM image in the middle shows that the surface of the base glass is smooth and flat, with uniform distribution of network formers (Si), modifiers (Ca), (Mg), etc., without obvious agglomeration, and has typical glassy characteristics; Figure 3 The BET data show that the basic glass sample has a low specific surface area due to the rapid densification of the structure during rapid cooling, while the hysteresis loop in its adsorption curve originates from the large-sized pores formed by the microcracks generated by the thermal stress of rapid cooling, which has typical glassy characteristics.
[0015] Example 2: A method for preparing basic glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag, the specific steps are as follows: (1) Grind and sieve the high calcium and low iron AOD stainless steel slag to obtain stainless steel slag powder with a particle size of less than 15 mesh; (2) Measure the chemical state and content of metal elements Cr, Ni, Fe, Mn, Ca, and Mg in stainless steel slag powder, as shown in Table 2; Table 2 Chemical states and contents of metal elements Cr, Ni, Fe, Mn, Ca, and Mg in stainless steel slag powder ; Determination of Cr in the chemical state by XPS 6+ 2% of total Cr; (3) According to the chemical state and content of the metal elements Cr, Ni, Fe, Mn, Ca, and Mg, the additives SiO2, MgO, and borax are added to the stainless steel slag powder to obtain a mixture A, and then ZrO2 and nano-Al2O3 are added to obtain a mixture B; specifically, the theoretical addition amount of borax is 20%±0.5% of the total mass of the metal elements Cr, Ni, Fe, and Mn; the addition amounts of SiO2 and MgO are adjusted according to the content of the metal elements Ca and Mg so that the molar ratio of CaO, MgO, and SiO2 is 1.33:1:1.80, the addition amount of ZrO2 is 1% of the total mass of the mixture A, and the addition amount of nano-Al2O3 is 2% of the total mass of the mixture A so that the mixture meets the composition range of diopside CaMgSi2O6; Calculated by mass fraction of stainless steel slag powder, the additive amounts of this embodiment are: SiO2 10%, MgO 20%, borax 1%; (4) Under a vacuum environment (40 Pa), the mixed material B is subjected to gradient temperature increase melting modification to obtain high-temperature modified slag; the gradient temperature increase melting modification method is as follows: uniformly heating the temperature to 1100°C at a heating rate of 12°C / min and keeping the temperature for 60 minutes, then uniformly heating the temperature to 1400°C at a heating rate of 7°C / min and keeping the temperature for 60 minutes; (5) Directly spraying atomized micron-sized water droplets onto the melt for atomized water quenching, so that the high-temperature modified slag is rapidly cooled to a temperature below 800°C within 1 to 10 seconds to obtain basic glass particles; The XRD pattern of the basic glass particles in this embodiment is shown in Figure 4 ,from Figure 4 It can be seen that there are no sharp diffraction peaks in the XRD pattern (especially in the high-angle region of 10-90°), indicating that the sample has not undergone obvious crystallization and is in an ideal basic glass state; Figure 5 The SEM-EDS image in the figure shows that the surface of the sample is dense and smooth as a whole, which is consistent with the glass phase structure formed during the rapid cooling (water quenching) process.
[0016] Example 3: A method for preparing basic glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag, the specific steps are as follows: (1) Grind and sieve the high calcium and low iron AOD stainless steel slag to obtain stainless steel slag powder with a particle size of less than 15 mesh; (2) The chemical state and content of the metal elements Cr, Ni, Fe, Mn, Ca, and Mg in the stainless steel slag powder were measured, as shown in Table 3; Table 3 Chemical states and contents of metal elements Cr, Ni, Fe, Mn, Ca, and Mg in stainless steel slag powder ; Determination of Cr in the chemical state by XPS 6+ 8% of total Cr (borax addition needs to be increased by 20%) (3) According to the chemical state and content of metal elements Cr, Ni, Fe, Mn, Ca, and Mg, additives SiO2, MgO, and borax are added to the stainless steel slag powder to obtain a mixture A, and then ZrO2 and nano-Al2O3 are added to obtain a mixture B; specifically, the theoretical addition amount of borax is 20%±0.5% of the total mass of the metal elements Cr, Ni, Fe, and Mn, and according to the determination of the chemical state of Cr in Cr, the amount of borax added is 20%±0.5% of the total mass of the metal elements Cr, Ni, Fe, and Mn. 6+ The amount of borax added is increased by 20% according to the content of metal elements Ca and Mg, and the amount of SiO2 and MgO added is adjusted to make the molar ratio of CaO, MgO and SiO2 1.06:1:2.42. The amount of ZrO2 added is 5% of the total mass of the mixture A, and the amount of nano-Al2O3 added is 8% of the total mass of the mixture A so that the mixture meets the composition range of diopside CaMgSi2O6. Calculated by mass fraction of stainless steel slag powder, the additive amounts added in this embodiment are: SiO2 80%, MgO 80%, and borax 6% (the theoretical amount is 5%, and then increased by 20%); (4) Under a vacuum environment (80 Pa), the mixed material B is subjected to gradient temperature increase melting modification to obtain high-temperature modified slag; the gradient temperature increase melting modification method is as follows: uniformly heating the temperature to 1000°C at a heating rate of 12°C / min and keeping the temperature for 150 minutes, then uniformly heating the temperature to 1400°C at a heating rate of 6°C / min and keeping the temperature for 90 minutes; (5) Directly spraying atomized micron-sized water droplets onto the melt for atomized water quenching, so that the high-temperature modified slag is rapidly cooled to a temperature below 800°C within 1 to 10 seconds to obtain basic glass particles; The XRD pattern of the basic glass particles in this embodiment is shown in Figure 6 ,from Figure 6 It can be seen that there are no sharp diffraction peaks in the XRD pattern (especially in the high-angle region of 10-90°), indicating that the sample has not undergone obvious crystallization and is in an ideal basic glass state.
[0017] Example 4: A method for preparing basic glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag, the specific steps are as follows: (1) Grind and sieve the high calcium and low iron AOD stainless steel slag to obtain stainless steel slag powder with a particle size of less than 15 mesh; (2) The chemical states and contents of the metal elements Cr, Ni, Fe, Mn, Ca, and Mg in the stainless steel slag powder were measured, as shown in Table 4. Table 4 Chemical states and contents of metal elements Cr, Ni, Fe, Mn, Ca, and Mg in stainless steel slag powder ; Determination of Cr in the chemical state by XPS 6+ 2% of total Cr; (3) According to the chemical state and content of the metal elements Cr, Ni, Fe, Mn, Ca, and Mg, the additives SiO2, MgO, and borax are added to the stainless steel slag powder to obtain a mixture A, and then ZrO2 and nano-Al2O3 are added to obtain a mixture B; specifically, the theoretical addition amount of borax is 20%±0.5% of the total mass of the metal elements Cr, Ni, Fe, and Mn; the addition amounts of SiO2 and MgO are adjusted according to the content of the metal elements Ca and Mg so that the molar ratio of CaO, MgO, and SiO2 is 0.95:1:1.89, the addition amount of ZrO2 is 3% of the total mass of the mixture A, and the addition amount of nano-Al2O3 is 4% of the total mass of the mixture A so that the mixture meets the composition range of diopside CaMgSi2O6; Calculated by mass fraction of stainless steel slag powder, the additive amounts of this embodiment are: SiO2 45%, MgO 30%, and borax 3%; (4) Under a vacuum environment (100 Pa), the mixed material B is subjected to gradient temperature increase melting modification to obtain high-temperature modified slag; the gradient temperature increase melting modification method is as follows: uniformly heating the temperature to 1200°C at a heating rate of 9°C / min and keeping the temperature for 50 minutes, then uniformly heating the temperature to 1450°C at a heating rate of 7°C / min and keeping the temperature for 120 minutes; (5) Directly spraying atomized micron-sized water droplets onto the melt for atomized water quenching, so that the high-temperature modified slag is rapidly cooled to a temperature below 800°C within 1 to 10 seconds to obtain basic glass particles; The XRD pattern of the basic glass particles in this embodiment is shown in Figure 7 ,from Figure 7 It can be seen that there are no sharp diffraction peaks in the XRD pattern (especially in the high-angle region of 10-90°), indicating that the sample has not undergone obvious crystallization and is in an ideal basic glass state.
[0018] The above describes the specific embodiments of the present invention in detail, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in this field without departing from the scope of the present invention.
Claims
1. A method for preparing basic glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag, characterized in that: The specific steps are as follows: (1) Grinding and sieving high calcium and low iron AOD stainless steel slag to obtain stainless steel slag powder; (2) Measure the chemical state and content of metal elements Cr, Ni, Fe, Mn, Ca, and Mg in stainless steel slag powder; (3) According to the chemical state and content of the metal elements Cr, Ni, Fe, Mn, Ca, and Mg, additives SiO2, MgO, and borax are added to the stainless steel slag powder to obtain mixed material A, and then ZrO2 and nano-Al2O3 are added to obtain mixed material B; (4) Under vacuum conditions, the mixed material B is subjected to gradient temperature increase and melting modification to obtain high-temperature modified slag; (5) Atomized micron-sized water droplets are sprayed onto the melt in a direction to perform atomized water quenching, so that the high-temperature modified slag is rapidly cooled to a temperature below 800°C within 1 to 10 seconds to obtain basic glass particles.
2. The method for preparing base glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag according to claim 1, characterized in that: Step (1) The particle size of the stainless steel slag powder is less than 20 mesh.
3. The method for preparing base glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag according to claim 1, characterized in that: In terms of mass percentage, the high calcium, low iron type AOD stainless steel slag in step (1) contains 40-60% CaO, 10-35% SiO2, 1-5% Al2O3, 2-15% MgO, and 0.1-2% Fe.
4. The method for preparing base glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag according to claim 1, characterized in that: Calculated by mass fraction of stainless steel slag powder, step (3) SiO2 10-80%, MgO 20-80%, borax 1-5%.
5. The method for preparing base glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag according to claim 4, characterized in that: The theoretical amount of borax added in step (3) is 20%±0.5% of the total mass of the metal elements Cr, Ni, Fe, and Mn and the Cr content in the chemical state of Cr is determined. 6+ When it accounts for more than 5% of the total Cr, the amount of borax added is increased by 20%; according to the content of metal elements Ca and Mg, the amount of SiO2 and MgO added is adjusted so that the molar ratio of CaO, MgO, and SiO2 is (0.8~1.2):1:(1.5~2.5), the amount of ZrO2 added is 1~5% of the total mass of the mixture A, and the amount of nano-Al2O3 added is 2~8% of the total mass of the mixture A so that the mixture meets the composition range of diopside CaMgSi2O6.
6. The method for preparing base glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag according to claim 1, characterized in that: Step (4) Gradient heating melt modification method: uniformly heat the temperature to 1000-1200°C at a heating rate of 8-15°C / min and keep warm for 30-150 min, then uniformly heat the temperature to 1250-1500°C at a heating rate of 6-8°C / min and keep warm for 30-120 min.
7. The method for preparing base glass by vacuum melting and atomizing water quenching of high-calcium, low-iron AOD stainless steel slag according to claim 1, characterized in that: The particle size of the basic glass particles in step (5) is 1 to 5 mm.